PL206672B1 - Fungicidal mixtures based on prothioconazole - Google Patents

Abstract

The invention relates to a fungicidal mixtures containing (1) 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione (prothioconazoles) of formula I or the salts or adducts thereof and at least one additional fungicide or salts or adducts thereof, selected from (2) fenpropiomorph of formula II and (3) tridemorph of formula III wherein n = 10, 11, 12, (60 - 70 %) or 13, and (4) fenpropidin of formula IV in a synergistically effective amount.

Description

(12) PATENT DESCRIPTION (21) Filing number: 372353 (19) PL (11) 206672 (13) B1 (22) Filing date: February 26, 2003 (86) Date and number of the international application:

February 26, 2003, PCT / EP03 / 001930 (87) International application publication date and number:

2003-09-12, WO03 / 073850 (51) Int.Cl.

A01N 43/653 (2006.01) A01N 43/84 (2006.01) A01N 43/40 (2006.01) A01P 3/00 (2006.01)

A fungicidal mixture based on prothioconazole, a method of combating harmful fungi and a fungicide (73).

BASF AKTIENGESELLSCHAFT, Ludwigshafen, DE (30) Priority:

01.03.2002, DE, 10208841.1 (43) Application announced:

11.07.2005 BUP 14/05 (45) The following was announced about the grant of the patent:

30.09.2010 WUP 09/10 (72) Inventor (s):

EBERHARD AMMERMANN, Heppenheim, DE REINHARD STIERL, Freinsheim, DE GISELA LORENZ, Neustad, DE

SIEGFRIED STRATHMANN, Limburgerhof, DE

KLAUS SCHELBERGER, Gonnheim, DE

V. JAMES SPADAFORA, Sugar Land, US THOMAS CHRISTEN, Dannstadt-Schauernheim, DE (74) Agent:

item. stalemate. Marshal Agnieszka

SULIMA * GRABOWSKA * SIERZPUTOWSKA Patent and Trademark Office, general partnership

PL 206 672 B1

Description of the invention

The subject matter is a prothioconazole-based fungicidal mixture, a method for combating harmful fungi and a fungicide.

The compound of formula I, i.e. 2- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro [1,2,4] triazole-3-thion (thioconazole ), is already known from WO96 / 16048.

A number of compositions of prothioconazole as active ingredient with a large number of other fungicidal compounds are disclosed in WO 98/47367.

Fenpropimorph of the formula II and its use as a plant protection agent are described in DE-A-2752135.

The tridemorph of formula III is also known and has been described in DE-A-1164152.

There is also known fenpropidin of formula IV, described in DE-A-2752096.

The object of the invention was to develop mixtures with improved activity against harmful fungi with a reduced total amount of active substances applied (synergistic mixtures), in order to reduce the application rates and improve the activity spectrum of the known compounds I, II, III and IV.

It has been found that this aim is achieved by mixtures of prothioconazole with at least one other fungicide as defined below. It has furthermore been found that by using compound I and at least one of the compounds II, III or IV simultaneously, i.e. together or separately, or by using compound I and at least one of the compounds II, III or IV sequentially, the harmful fungi can be better controlled than with the use of each of these compounds.

The invention therefore relates to a fungicidal mixture, characterized in that it comprises (1) 2- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro [1,2,4 ] triazole-3-thion (prothioconazole) of the formula I, or a salt or adduct thereof

and at least one other fungicide, or a salt or adduct thereof selected from the group consisting of (2) fenpropiomorph of formula II

and (3) a tridemorph of formula III

n = 10, 11, 12 (60 - 70%) or 13

PL 206 672 B1 i

(4) fenpropidin of formula IV

in a synergistically effective amount.

Preferably, the fungicidal mixture according to the invention comprises prothioconazole of formula I and fenpropimorph of formula II.

Furthermore, it is preferred that the fungicidal mixture according to the invention comprises a prothioconazole of formula I and a tridemorph of formula III.

Furthermore, it is preferred that the fungicidal mixture according to the invention comprises prothioconazole of formula I and fenpropidin of formula IV.

Preferably in the fungicidal mixture according to the invention the weight ratio of prothioconazole of the formula I to

- fenpropimorph of formula II ranges from 20: 1 to 1:20,

- the tridemorph of formula III ranges from 20: 1 to 1:20, and

- fenpropidin of formula IV ranges from 20: 1 to 1:20.

Furthermore, the invention relates to a method for controlling harmful fungi, characterized in that harmful fungi, their growth sites or plants, seeds, soil, surfaces, materials or spaces to be kept fungus-free are treated with a fungicidal mixture as defined above.

Preferably, in the process according to the invention, a compound of formula I as defined above and at least one compound of formula II, III or IV as defined above are applied simultaneously, i.e. together or separately, or sequentially.

Preferably, in the process according to the invention, the above-defined fungicidal mixture or the above-defined compound of formula I with at least one compound of formula II, III or IV as defined above is applied in an amount of 0.01 to 8 kg / ha.

Furthermore, the invention relates to a fungicide, characterized in that it comprises a fungicidal mixture as defined above and a solid or liquid carrier.

2- [2- (1-Chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro [1,2,4] triazole-3-thion of formula I is known from WO 96- 16048. This compound may exist in the form of "thion of the formula."

or in tautomeric form "mercapto of the formula

PL 206 672 B1

For the sake of simplicity, only the form "tiono. Is shown in each case." Fenpropiomorph of formula II

is known from DE-A-2752135.

n = 10, 11, 12 (60-70%) or 13 is described in DE-A-1164125. Fenpropidin of formula IV

is known from DE-A-2752096.

Due to the basic nature of their nitrogen atoms, the compounds I to IV are capable of forming salts or adducts with inorganic and organic acids or with metal ions.

Examples of inorganic acids are halogen acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, sulfuric acid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic, oxalic acid, alkylsulfonic acids (sulfonic acids with straight or branched alkyl groups with 1 - 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic groups such as phenyl or naphthyl bound to one or two sulfonic acid groups), acids alkylphosphonic acids (phosphonic acids with straight or branched alkyl groups with 1 - 20 carbon atoms), arylphosphonic acids or aryl diphosphonic acids (aromatic groups such as phenyl or naphthyl bonded to one or two phosphoric acid groups) in which the alkyl or aryl groups are optionally substituted with additional substituents, e.g. p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid you, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

Suitable metal ions are, in particular, the ions of the elements of the second main group, especially calcium and magnesium, of the third and fourth main groups, especially aluminum, tin and lead, and of the first to eighth transition groups, especially chromium, manganese, iron, cobalt, nickel, copper, zinc and others. Metal ions of the elements of the transition groups of the fourth period of the periodic table are especially preferred. Metals can have the various valences inherent in them.

As stated above, mixtures of prothioconazole with fenpropimorph are preferred.

PL 206 672 B1

In addition, mixtures of prothioconazole with tridemorph are preferred.

Mixtures of prothioconazole with fenpropidin are preferred.

Ternary mixtures of prothioconazole with two other fungicides mentioned above are also preferred.

In preparing the mixtures, it is preferable to use pure active compounds I, II, III and IV to which other compounds can be added active against harmful fungi or against other pests such as insects, arachnids or nematodes, as well as herbicidally active substances or plant growth regulators or fertilizers.

Mixtures of compound I and at least one of the compounds II, III or IV or compound I and at least one of the compounds II, III and IV used simultaneously, together or separately, are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of Ascomycetes , Basidiomycetes, Phycomycetes, and Deuteromycetes. Some of them are systemic and can be used in plant protection as foliar and soil fungicides.

These compounds are of particular importance in controlling a wide variety of fungi on a wide variety of crops, such as cotton, vegetables (e.g. cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass, oats, bananas, coffee, corn, fruit trees, rice, rye, soybeans, grapevines, wheat, ornamentals, and sugarcane, and on the seeds of many plants.

They are particularly suitable for the control of the following phytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, Podosphaera leucotricha on apple trees, Uncinula necator on grapevines, Puccinia species in cereals, Rhizoctonia species in on lawns, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apple trees, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinera (gray mold) on strawberries, vegetables, ornamentals and vines, Cercospora arachidicola on peanuts , Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on grapevines, Pseudoperonospora species on hops and cucumbers, Alternaria species on vegetables and fruit trees, and Mycospanerelus species on Fusarium and Mycospanerel species. erticillium.

Furthermore, these compounds are suitable for the protection of materials (e.g. for the protection of wood), for example against Paecilomyces variotii.

Compound I and at least one of the compounds II, III and IV can be applied simultaneously, i.e. jointly or separately, or sequentially, the order of separate application generally not having any effect on the control effect.

The compounds I and II are usually used in a weight ratio of 20: 1 to 1:20, especially 10: 1 to 1:10, preferably 5: 1 to 1: 5.

The compounds I and III are usually used in a weight ratio of 20: 1 to 1:20, especially 10: 1 to 1:10, preferably 5: 1 to 1: 5.

The compounds I and IV are usually used in a weight ratio of 20: 1 to 1:20, especially 10: 1 to 1:10, preferably 5: 1 to 1: 5.

Depending on the desired effect, the application rates of the mixtures according to the invention are, in particular in cultivated areas, from 0.01 to 8 kg / ha, preferably from 0.1 to 5 kg / ha, in particular from 0.1 to 3.0 kg. / ha.

The application rates for the compound I are from 0.01 to 1 kg / ha, preferably from 0.05 to 0.5 kg / ha, in particular from 0.05 to 0.3 kg / ha.

Correspondingly, the application rates for the compound II are from 0.01 to 1 kg / ha, preferably from 0.02 to 0.5 kg / ha, in particular from 0.05 to 0.3 kg / ha.

Correspondingly, the application rates for the compound III are from 0.01 to 1 kg / ha, preferably from 0.02 to 0.5 kg / ha, in particular from 0.05 to 0.3 kg / ha.

Correspondingly, the application rates for the compound IV are from 0.01 to 1 kg / ha, preferably from 0.02 to 0.5 kg / ha, in particular from 0.05 to 0.3 kg / ha.

For seed treatment, the application rates of the mixture are generally from 0.001 to 250 g / kg of seed, preferably from 0.01 to 100 g / kg, in particular from 0.01 to 50 g / kg.

In the case of controlling phytopathogenic harmful fungi on plants, separate or joint application of compound I and at least one of the compounds II, III and IV or of mixtures of compound I and at least one of the compounds II, III and IV is used by spraying or dusting the seeds, plants or the soil before or after sowing the plants, or before or after the emergence of the plants.

PL 206 672 B1

The fungicidal synergistic mixtures according to the invention or the compound I and at least one of the compounds II, III and IV can be formulated, for example, in the form of solutions for direct application of spray liquids, powders and suspensions or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions. , oil dispersions, pastes, dusts, sprinkling preparations or granules and apply them by spraying, spraying, dusting, scattering or pouring. The form used depends on the intended purpose; in any case, it should ensure the finest and most even distribution of the mixture according to the invention.

The formulations are prepared by known methods, for example by adding solvents and / or carriers. Usually, inert additives such as emulsifiers or dispersants are added to the formulations.

Suitable surfactants are alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, e.g. lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, as well as fatty acids, alkyl and alkylarylsulfonates, alkyl ether sulfates, and alkyl ether sulfates. fatty alcohols and salts of sulphated hexa-, hepta- and octadecanols or glycol ethers and fatty alcohols, condensation products of sulphonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulphonic acids with phenol and formaldehyde, polyoxyethylene glycol ether, ethoxylated isophenol ethoxylate octyl- or nonylphenol, polyglycol alkylphenyl ethers or polyglycol tributylphenyl ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensation products, ethoxylated castor oil, ethers a alkyl polyoxyethylene or polyoxypropylene, polyglycol ether of lauryl alcohol, sorbitan esters, lignin sulfite liquors or methylcellulose.

Powders, sprinklers and dusts can be prepared by mixing or co-grinding compound I and at least one of compounds II, III and IV or a mixture of compound I and at least one of compounds II, III and IV with a solid carrier.

Granules (e.g. coated, impregnated or homogeneous granules) are usually prepared by binding the active ingredient or ingredients to a solid carrier.

Examples of fillers or solid carriers are mineral earths such as silica gels, silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus clay, loess, clay, dolomite, diatomaceous earth, calcium sulphate, magnesium sulphate, oxide magnesium, ground synthetic materials and fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, and vegetable products such as grain flour, tree bark flour, wood flour, ground nut shell, powdered cellulose or other solid carriers.

In general, the formulations contain from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of compound I and at least one of the compounds II, III and IV or a mixture of compound I and at least one of the compounds II, III and IV. The active substances are used as compounds in a purity of 90% to 100%, preferably 95% to 100% (according to NMR or HPLC spectra).

Compounds I, II, III and IV in mixtures or suitable formulations are applied by treating the harmful fungi, their locus or plants, seeds, soil, areas, materials or spaces to be free of them, with a fungicidally effective amount of the mixture or compound I and at least one of the compounds II, III and IV in the case of separate application.

Application can be made before or after infection by the harmful fungi.

Application example

The synergistic effect of the mixtures according to the invention has been demonstrated in the following tests:

The active ingredients were formulated separately or together as a 10% emulsion in a mixture of 63% by weight. % of cyclohexanone and 27 wt. emulsifier and diluted with water to obtain the desired concentration.

Assessment was carried out by determining the infested leaf area in%. These percentages were converted to efficacy. Efficacy (W) according to Abbot's formula was calculated as follows:

W = (1 - α / β) X 100 a corresponds to the infestation of the plants treated with the fungi in%, and β corresponds to the infestation of untreated plants (control plants) by the fungi in%.

An efficacy of 0 means that the degree of infection of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.

The expected efficacy of the active substance mixtures was determined according to the Colby formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficacy.

PL 206 672 B1

Colby's formula:

E = x + y - x y / 100

E Expected efficacy in% for an untreated control when using a mixture of Active A and B in concentrations a and bx Efficiency in% for the untreated control when using Active A in a concentration of yy Efficiency in% for to untreated control in case of using active substance B at concentration b.

Application example 1: Efficacy against wheat powdery mildew caused by Erysiphe [syn. Blumeria] graminis forma specialis tritici

Leaves of "Kanzler" wheat seedlings grown in pots were sprayed to runoff point with an aqueous suspension with the concentration of active substances given below. The suspension or emulsion was prepared from a stock solution containing 10% of the active ingredient in a mixture of 85% cyclohexanone and 5% emulsifier. 24 hours after the spray layer had dried on, the leaves were infected with spores of wheat powdery mildew (Erysiphe [syn. Blumeria] graminis forma specialis tritici). The test plants were placed in a greenhouse at a temperature of 20-24 ° C and a relative air humidity of 60-90%. After 7 days, the extent of the development of powdery mildew was assessed visually as percentage infection of the total leaf area.

The visually determined percent leaf area infection was converted to% efficacy with respect to untreated controls. An efficacy of 0 means the same level of infestation as the untreated control, an efficacy of 100 means an infestation of 0%. The expected efficacy values for the active ingredient compositions were determined according to the above Colby formula and compared with the observed efficacy values.

T a b e l a 1

The active substance Concentration of active ingredient in the spray liquid in ppm Efficacy in% against untreated control Control sample (untreated) (77% of electrocution) 0 Compound I = prothioconazole 1 0 0.25 0 Compound II = fenpropimorph 2.5 74 0.6 0 0.15 0 Compound III = tridemorph 2.5 48 0.6 0 0.15 0 Compound IV = fenpropidin 0.6 61 0.15 0

T a b e l a 2

Compositions according to the invention Effectiveness established Efficiency calculated *) 1 2 3 Compound I = prothioconazole + compound II = fenpropimorph 0.25 + 2.5 ppm; 1: 10 mixture 87 74 Compound I = prothioconazole + compound II = fenpropimorph 1 + 2.5 ppm; 1: 2.5 mixture 87 74 Compound I = prothioconazole + compound II = fenpropimorph 0.25 + 0.6 ppm; 1: 2.5 mixture 35 0

PL 206 672 B1 cont. table 2

1 2 3 Compound I = prothioconazole + compound II = fenpropimorph 1 + 0.6 ppm; 1: 1.6 mixture 74 0 Compound I = prothioconazole + compound II = fenpropimorph 0.25 + 0.15 ppm; 1: 1.6 mixture 48 0 Compound I = prothioconazole + compound III = tridemorph 0.25 + 2.5 ppm; 1: 10 mixture 61 48 Compound I = prothioconazole + compound III = tridemorph 1 + 2.5 ppm; 1: 2.5 mixture 99 48 Compound I = prothioconazole + compound III = tridemorph 0.25 + 0.6 ppm; 1: 2.5 mixture 61 0 Compound I = prothioconazole + compound III = tridemorph 1 + 0.6 ppm; 1: 1.6 mixture 74 0 Compound I = prothioconazole + compound III = tridemorph 0.25 + 0.15 ppm: 1: 1.6 mixture 87 0 Compound I = prothioconazole + compound IV = fenpropidin 0.25 + 0.6 ppm; 1: 2.5 mixture 100 61 Compound I = prothioconazole + compound III = tridemorph 1 + 0.6 ppm; 1: 1.6 mixture 100 61 Compound I = prothioconazole + compound III = tridemorph 0.25 + 0.15 ppm; 1: 1.6 mixture 81 0

*) Efficiency calculated according to Colby's formula

The test results show that the found efficacy of the mixtures at all ratios was higher than the efficacy calculated according to the Colby formula (with Synerg 173. XLS).

Application example 2: Healing effect against wheat brown rust caused by Puccinia recondita

Leaves of 'Kanzler' wheat seedlings growing in pots were dusted with spores of brown rust (Puccinia recondita). The pots were then placed in a highly humid atmosphere (90-95%) chamber at 20-22 ° C for 24 hours. During this time, the spores germinated and the hyphae penetrated the leaf tissue. The next day, the infected plants are sprayed to run-off point with an aqueous preparation of active compound at the concentration given below. A suspension or emulsion was made from a stock solution containing 10% active ingredient, 85% cyclohexanone, and 5% emulsifier. After the spray layer had dried on, the test plants were placed in a greenhouse at 20-22 ° C and 65-70% relative air humidity for 7 days. The severity of rust development on the leaves was then assessed visually.

The visually determined percent leaf area infection was converted to% efficacy with respect to untreated controls. An efficacy of 0 means the same level of infestation as the untreated control, an efficacy of 100 means an infestation of 0%. The expected efficacy values for the active ingredient compositions were determined according to the above Colby formula and compared with the reported efficacy values.

PL 206 672 B1

T a b e l a 3

The active substance Concentration of active ingredient in the spray liquid in ppm Efficacy in% against untreated control Control sample (untreated) (90% infection) 0 Compound I = prothioconazole 1 78 0.25 22 Compound II = fenpropimorph 2.5 22 0.6 0 0.15 0 Compound III = tridemorph 2.5 0 0.6 0 0.15 0 Compound IV = fenpropidin 2.5 44 0.6 0 0.15 0

T a b e l a 4

Compositions according to the invention Effectiveness established Efficiency calculated *) 1 2 3 Compound I = prothioconazole + compound II = fenpropimorph 0.25 + 2.5 ppm; 1: 10 mixture 55 44 Compound I = prothioconazole + compound II = fenpropimorph 1 + 2.5 ppm; 1: 2.5 mixture 92 83 Compound I = prothioconazole + compound II = fenpropimorph 0.25 + 0.6 ppm; 1: 2.5 mixture 44 22 Compound I = prothioconazole + compound II = fenpropimorph 1 + 0.6 ppm; 1: 1.6 mixture 94 78 Compound I = prothioconazole + compound II = fenpropimorph 0.25 + 0.15 ppm; 1: 1.6 mixture 44 22 Compound I = prothioconazole + compound III = tridemorph 0.25 + 2.5 ppm; 1: 10 mixture 44 22 Compound I = prothioconazole + compound III = tridemorph 1 + 2.5 ppm; 1: 2.5 mixture 92 78 Compound I = prothioconazole + compound III = tridemorph 0.25 + 0.6 ppm; 1: 2.5 mixture 44 22 Compound I = prothioconazole + compound III = tridemorph 1 + 0.6 ppm; 1: 1.6 mixture 89 78 Compound I = prothioconazole + compound III = tridemorph 0.25 + 0.15 ppm; 1: 1.6 mixture 44 22 Compound I = prothioconazole + compound IV + fenpropidin 0.25 + 2.5 ppm; 1: 10 mixture 78 57

PL 206 672 B1 cont. table 4

1 2 3 Compound I = prothioconazole + compound III = tridemorph 0.25 + 0.6 ppm; 1: 2.5 mixture 44 22 Compound I = prothioconazole + compound III = tridemorph 1 + 0.6 ppm; 1: 1.6 mixture 97 78 Compound I = prothioconazole + compound III = tridemorph 0.25 + 0.15 ppm; 1: 1.6 mixture 33 22

*) Efficiency calculated according to Colby's formula

The test results show that the found efficacy of the mixtures at all ratios was higher than the efficacy calculated according to the Colby formula (with Synerg 173. XLS).

Claims (9)

Patent claims CLAIMS 1. A fungicidal mixture comprising (1) 2- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro [1,2,4] triazole -3-thion (prothioconazole) of formula I, or a salt or adduct thereof, and at least one other fungicide, or a salt or adduct thereof selected from the group consisting of (2) fenpropiomorph of formula II and (3) tridemorph of formula III n = 10, 11, 12 (60 - 70%) or 13 PL 206 672 B1 i (4) fenpropidin of Formula IV in a synergistically effective amount. 2. The fungicidal mixture according to claim 1 The composition of claim 1, comprising prothioconazole of formula I and fenpropimorph of formula II. 3. The fungicidal mixture according to claim 1 The composition of claim 1, comprising the prothioconazole of the formula I and the tridemorph of the formula III. 4. The fungicidal mixture according to claim 1 The composition of claim 1, comprising prothioconazole of formula I and fenpropidin of formula IV. 5. The fungicidal mixture according to claim 1 The composition of claim 1, wherein the weight ratio of prothioconazole of formula I to - fenpropimorph of formula II ranges from 20: 1 to 1:20, - the tridemorph of formula III ranges from 20: 1 to 1:20, and - fenpropidin of formula IV ranges from 20: 1 to 1:20. Method for controlling harmful fungi, characterized in that the harmful fungi, their growth sites or plants, seeds, soil, surfaces, materials or spaces to be kept fungus-free are treated with a fungicidal mixture as defined in claim 1. 1. 7. The method according to p. 6. A compound according to claim 6, characterized in that the compound of formula I as defined in claim 1 1 and at least one compound of formula II, III or IV as defined in claim 1 1 is applied simultaneously, that is, together or separately, or sequentially. 8. The method according to p. A fungicidal mixture or a compound of formula I as defined in claim 6 or 7. With at least one compound of formula II, III or IV as defined in claim 1 with at least one compound of formula II, III or IV. 1 is applied in an amount of 0.01 to 8 kg / ha. 9. A fungicide, characterized in that it comprises a fungicidal mixture as defined in any one of the preceding claims. 1 and a solid or liquid carrier.